JP2006265106A - Method for producing alcoholate compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a 2-cyanomethyl-2-adamantyl ester compound which is a new compound useful as a raw material monomer for functional materials and electronic materials. <P>SOLUTION: For example, an alcoholate compound obtained by reacting a 2-adamantanone compound with acetonitrile in the presence of an organometallic compound is reacted with a polymerizable unsaturated carboxylic acid anhydride such as methacrylic acid anhydride or a polymerizable unsaturated carboxylic acid halide such as methacrylic acid chloride to produce the 2-cyanomethyl-2-adamantyl ester compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention uses a method for producing an alcoholate compound useful as a raw material for synthesizing 2-cyanomethyl-2-adamantyl ester compounds useful as raw material monomers for functional materials and electronic materials, and an alcoholate compound obtained by the method. The present invention relates to a method for producing a 2-cyanomethyl-2-adamantyl ester compound.

  Since adamantane derivatives have excellent heat resistance and transparency, they are expected to be applied to highly functional materials such as heat resistant polymers and electronic materials such as semiconductor resists. Among them, an adamantyl ester compound having a polymerizable unsaturated hydrocarbon group is an extremely useful compound used alone or together with other monomers as a raw material monomer for a polymer material or a resist material (see Patent Document 1). When such a polymerizable adamantyl ester compound is used as a resist material, a plurality of monomers having different polarities are used, and the polarity of the resist resin is controlled by changing the composition of the monomer composition to dissolve it in various solvents. Control of physical properties such as properties is performed. Examples of the known polymerizable adamantyl ester compounds include 2-alkyl-2-adamantyl (meth) acrylate and 3-hydroxy-1-adamantyl (meth) acrylate (see Patent Documents 1 and 2). There are not so many kinds.

Japanese Patent Laid-Open No. 10-182552 JP-A-63-33350

  From the viewpoint of expanding the degree of freedom in designing the physical properties of resist resins, it is required to provide various types of polymerizable adamantyl ester compounds. The present inventors have conceived of introducing a cyano group into the polymerizable adamantyl ester compound in order to meet such a demand. This is based on the idea that if a cyano group, which is a polar group, is introduced, the polarity can be changed over a wide range depending on the position of introduction and combinations with other substituents. The present inventors paid attention to the 2-cyanomethyl-2-adamantyl ester compound from the similarity of the skeleton to the known polymerizable adamantyl ester compound, but such a compound has not been known so far.

  Conventionally, as a method for producing a polymerizable unsaturated carboxylic acid adamantyl ester compound having an alkyl group and a polymerizable group at the 2-position of an adamantane ring such as 2-alkyl-2-adamantyl (meth) acrylate, an adamantane compound and an alkyl lithium Alternatively, a method of reacting with alkylmagnesium bromide and then dropping (meth) acryloyl chloride is known (see Patent Document 1).

  In order to synthesize the compound having a cyanomethyl group by applying such a method, it is necessary to use a cyanomethyl alkali metal salt obtained by substituting the hydrogen of the methyl group of acetonitrile with an alkali metal. Such cyanomethyl alkali metal salts are not described.

  As a method for synthesizing a cyanomethyl alkali metal salt, a method of reacting acetonitrile and n-butyllithium at −80 ° C. (for example, The Journal of Organic Chemistry, 1968, Vol. 33, page 3402), acetonitrile and lithium A method of reacting diisopropylamide at −70 ° C. (for example, Synthesis, 1979, page 463) is known. In the former, a condensate with benzophenone is obtained in 89% yield using the cyanomethyl alkali metal salt obtained by such a method, and in the latter, a condensate with acetone is obtained in 49% yield. Have gained. Probably because the metal salt is unstable, the reaction temperature in both of the above reactions is an extremely low temperature of −70 ° C. or lower. From this, it is expected that special equipment such as cooling equipment is required when cyanomethyl alkali metal salt is used as a reaction raw material.

  Under such circumstances, an object of the present invention is to provide a method for efficiently producing a novel compound, 2-cyanomethyl-2-adamantyl ester compound.

  The present inventors have intensively studied to solve the above problems. As a result, the 2-cyanomethyl-2-adamantyl ester compound was efficiently produced by using an alcoholate of 2-cyanomethyl-2-adamantanol compound obtained by reacting an adamantanone compound and acetonitrile in the presence of an organometallic compound as a raw material. It has been successfully obtained and has led to the completion of the present invention.

  That is, the first present invention is represented by the following formula (1):

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A is an alkali metal.)
A process for producing an alcoholate compound represented by
Following formula (2)

{Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as those in the formula (1). }
And an adamantanone compound represented by formula (3):

(In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A is an alkali metal.)
A process for producing an alcoholate compound, comprising the step of reacting with an organometallic compound represented by the formula:

  The second aspect of the present invention is the following formula (4).

{Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as those in formula (1), and R ⁷ represents a polymerizable unsaturated hydrocarbon group which may have a substituent. is there. }
A process for producing a 2-cyanomethyl-2-adamantyl ester compound represented by formula (1), wherein the alcoholate compound represented by the formula (1) and a polymerizable unsaturated carboxylic acid anhydride or polymerizable compound are represented by the method of the first invention. A method for producing a 2-cyanomethyl-2-adamantyl ester compound, comprising a step of reacting with an unsaturated carboxylic acid halide.

  According to this method, the target product can be obtained efficiently without requiring an extremely low temperature of −70 ° C. or lower.

  The 2-cyanomethyl-2-adamantyl ester compound, which is the target product, is purified by crystallization on the back of having the characteristics of excellent solubility in a wide range of polar organic solvents from high polarity to low polarity as described above. Turned out to be difficult. In the production method of the present invention, the crude product of the 2-cyanomethyl-2-adamantyl ester compound represented by the above formula (4) obtained in the reaction step is used as a crystallization solvent with a mixed solvent of alcohol and water. By further including a purification step for purification by crystallization, a high-purity target product can be obtained efficiently.

  1st this invention provides the manufacturing method of the alcoholate compound useful as a synthetic | combination raw material of the said 2-cyanomethyl-2-adamantyl ester compound, It is an outstanding manufacturing method which does not require the cryogenic temperature below -70 degreeC. is there. In addition, according to the production method of the second invention using the compound obtained by the method, a high molecular weight impurity component having a molecular weight of about 300 to 5,000 (hereinafter, the impurity component is also referred to as “oligomer impurity”). It is possible to produce a 2-cyanomethyl-2-adamantyl ester compound in a high yield in a state where the production (by-product) of is highly suppressed.

  In 1st this invention, it shows by the said Formula (1) by including the process with which the adamantanone compound shown by said Formula (2), acetonitrile, and the organometallic compound shown by said Formula (3) are made to react. To produce an alcoholate compound. Hereinafter, reactants (reactant: reaction raw materials, catalysts, etc.), reaction conditions, reaction procedures, etc. used in the method will be described in detail.

(Adamantanone compound)
In the present invention, an adamantanone compound represented by the following formula (2) (hereinafter also referred to as a 2-adamantanone compound) is used as a raw material.

In the formula (2), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t-butyl group. , N-pentyl group, sec-pentyl group, isopentyl group and the like.

  Specific examples of 2-adamantanone compounds that can be suitably used in the present invention include 2-adamantanone, 1-methyl-2-adamantanone, 5-methyl-2-adamantanone, 1,3-dimethyl- Examples thereof include 2-adamantanone, 1,5-dimethyl-2-adamantanone, 5,7-dimethyl-2-adamantanone, 1,5,7-trimethyl-2-adamantanone and the like. Among these compounds, 2-adamantanone and 5,7-dimethyl-2-adamantanone are preferable from the viewpoint of the usefulness of the product.

(Organic metal compound)
The organometallic compound used as a raw material in the present invention is represented by the following formula (3).

In Formula (3), R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A is an alkali metal.

Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t-butyl group. , An n-pentyl group, a sec-pentyl group, an isopentyl group, and the like. Among these, an isopropyl group is particularly preferred because of its availability and high reactivity. The substituents for R ⁵ and R ⁶ may be different or the same, but are preferably the same from the viewpoint of availability.

  Moreover, as an alkali metal of A, although a well-known thing can be used without a restriction | limiting, it is preferable that it is lithium, sodium, or potassium from the ease of acquisition. Among these, lithium is particularly preferable because the danger of the alkali metal used is relatively low.

  Specific examples of the organic metal compound represented by the formula (3) are lithium amide, lithium monomethyl amide, lithium dimethyl amide, sodium amide, sodium monomethyl amide, sodium dimethyl amide, potassium amide, potassium. Monomethylamide, potassium dimethylamide, lithium monoethylamide, lithium diethylamide, lithium ethylmethylamide, sodium monoethylamide, sodium diethylamide, sodium ethylmethylamide, potassium monoethylamide, potassium diethylamide, potassium ethylmethylamide, lithium n-propyl Amide, lithium di-n-propylamide, lithium diisopropylamide, lithium n-propylisopropylamide, lithium isop Pyrmethylamide, lithium isopropylethylamide, sodium n-propylamide, sodium di-n-propylamide, sodium diisopropylamide, sodium n-propylisopropylamide, sodium isopropylmethylamide, sodium isopropylethylamide, potassium n-propylamide, potassium di n-propylamide, potassium diisopropylamide, potassium n-propylisopropylamide, potassium isopropylmethylamide, potassium isopropylethylamide, lithium n-butyramide, lithium sec-butyramide, lithium t-butylamide, lithium di-n-butyramide, lithium disec-butyramide Lithium di-t-butyramide, lithium isopropyl n-butyramide, Thium isopropyl sec-butyramide, lithium isopropyl t-butyramide, sodium n-butyramide, sodium isobutyramide, sodium t-butyramide, sodium di n-butyramide, sodium di sec-butyramide, sodium di t-butyramide, sodium isopropyl n-butyramide, Sodium isopropyl sec-butyramide, sodium isopropyl t-butyramide, potassium n-butyramide, potassium sec-butyramide, potassium t-butyramide, potassium di-n-butyramide, potassium disec-butyramide, potassium di-t-butyramide, potassium isopropyl n-butyramide, potassium isopropyl sec-Butylamide, Potassium isopropyl t-Butylamide Lithium n-pentylamide, lithium sec-pentylamide, lithium isopentylamide, lithium di n-pentylamide, lithium disec-pentylamide, lithium diisopentylamide, lithium isopropyl n-pentylamide, lithium isopropyl sec-pentylamide, Lithium isopropyl isopentylamide, sodium n-pentylamide, sodium sec-pentylamide, sodium isopentylamide, sodium di n-pentylamide, sodium disec-pentylamide, sodium diisopentylamide, sodium isopropyl n-pentylamide, Sodium isopropyl sec-pentylamide, sodium isopropylisopentylamide, potassium n-pentylamide, potash sec-pentylamide, potassium isopentylamide, potassium di-n-pentylamide, potassium disec-pentylamide, potassium diisopentylamide, potassium isopropyl n-pentylamide, potassium isopropyl sec-pentylamide, potassium isopropylisopentylamide, etc. It is done. Of these, lithium diethylamide, lithium di-n-propylamide, and lithium diisopropylamide are preferable, and lithium diisopropylamide is particularly preferable because of availability and high reactivity.

  As the above-mentioned organometallic compound, commercially available compounds can be used without particular limitation, but naturally synthesized compounds can also be used. For example, when synthesizing lithium diisopropylamide, a method of reacting lithium with a styrene monomer and diisopropylamine in an organic solvent (for example, The Journal of Organic Chemistry, Vol. 58, 1993, p. 1), n-butyl A method of reacting lithium and diisopropylamine in an organic solvent (for example, Tetrahedron, Vol. 36, page 775) can be employed. According to such a method, the organometallic compound can be obtained almost quantitatively.

  The amount of the organometallic compound used in the method of the present invention is not particularly limited, but 1 to 10 mol, particularly 1 to 5 mol, is used with respect to 1 mol of the 2-adamantanone compound because of ease of post-treatment. Is preferred.

(Acetonitrile)
The amount of acetonitrile used is not particularly limited, but it is preferable to use 1 to 10 mol, particularly 1 to 5 mol, per 1 mol of 2-adamantanone compound from the viewpoint of ease of post-treatment.

(Reaction conditions and reaction procedure)
The reaction of the 2-adamantanone compound according to the first aspect of the present invention, acetonitrile, and the organometallic compound represented by the formula (3) is performed by mixing these raw materials. From the viewpoint of easy control of reaction conditions and yield, the above reaction is preferably carried out in an organic solvent. Known organic solvents can be used without limitation, but diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, ethylene glycol dimethyl ether from the viewpoint of easy availability and a large amount of the desired product. Ethers such as hexane, heptane, octane and cyclohexane; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; aromatics such as benzene, toluene and xylene It is preferable to use hydrocarbons and the like. Among these, it is particularly preferable to use at least one selected from the group consisting of diethyl ether, di-n-butyl ether, and tetrahydrofuran. These organic solvents may be used as a mixture of two or more. Although the usage-amount of an organic solvent is not restrict | limited in particular, It is preferable to use 1-100 mass parts with respect to 1 mass part of 2-adamantanone compound, especially 2-50 mass parts from the ease of post-processing.

  The above reaction can be suitably performed, for example, by introducing a predetermined amount of each reactant (reactant) or solvent into the reaction vessel while stirring the temperature and stirring. At this time, the order of introduction of the reactants is not particularly limited, but when the organometallic compound and the 2-adamantanone compound are contacted at a high concentration, the 2-adamantanone compound is reduced and the 2-adamantanol compound is produced as a by-product. Alternatively, since a compound obtained by condensing an organometallic compound and a 2-adamantanone compound is by-produced, it is preferable to add the organometallic compound to a solution of acetonitrile and 2-adamantanone compound.

  The reaction can be carried out under pressure, under reduced pressure, or under normal pressure, but it is preferable to carry out under normal pressure for simplicity. In this reaction, if water is mixed in the reaction solution, a side reaction occurs, which is not preferable. Therefore, after sufficiently substituting with an inert gas such as nitrogen or argon, the reaction is performed while venting the inert gas. Is preferred.

  The reaction temperature of the above reaction is preferably −50 ° C. to 70 ° C., particularly preferably −30 to 40 ° C. from the viewpoint of suppressing by-products. The reaction time may be appropriately determined while confirming the progress of the reaction according to other reaction conditions, but a sufficient conversion rate can usually be obtained in 0.5 hours to 24 hours.

(Alcoholate compound)
By the above reaction, an alcoholate compound represented by the following formula (1) can be obtained.

In Formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A is an alkali metal. Each substituent and A are uniquely determined by the compound used as a raw material.

  Specific examples of the alcoholate represented by the formula (1) include lithium 2-cyanomethyl-2-adamantanolate, sodium 2-cyanomethyl-2-adamantanolate, potassium 2-cyanomethyl- 2-adamantanolate, lithium 2-cyanomethyl-1-methyl-2-adamantanolate, sodium 2-cyanomethyl-1-methyl-2-adamantanolate, potassium 2-cyanomethyl-1-methyl-2-adamantanolate Lithium 2-cyanomethyl-5-methyl-2-adamantanolate, sodium 2-cyanomethyl-5-methyl-2-adamantanolate, potassium 2-cyanomethyl-5-methyl-2-adamantanolate, lithium 2-cyanomethyl -1,3-Dimethyl-2-adamantanoler Sodium 2-cyanomethyl-1,3-dimethyl-2-adamantanolate, potassium 2-cyanomethyl-1,3-dimethyl-2-adamantanolate, lithium 2-cyanomethyl-5,7-dimethyl-2-adamantanoate Sodium 2-cyanomethyl-5,7-dimethyl-2-adamantanolate, potassium 2-cyanomethyl-5,7-dimethyl-2-adamantanolate, lithium 2-cyanomethyl-1,5,7-trimethyl-2 -Adamantanolate, sodium 2-cyanomethyl-1,5,7-trimethyl-2-adamantanolate, potassium 2-cyanomethyl-1,5,7-trimethyl-2-adamantanolate, etc. Among them, lithium 2-cyanomethyl-2-adamantanoler is particularly easy to synthesize. , Lithium 2-cyanomethyl-5,7-dimethyl-2-adamantanol Tano alert is preferred.

  The production of the target alcoholate by such a reaction can be indirectly confirmed by the production of an alcohol compound having a corresponding structure as a hydrolysis product. If an alcohol compound having a structure corresponding to the reaction system and hydrolysis mechanism is produced by hydrolysis, there is no doubt that the alcoholate represented by the formula (1) is produced. Although it is possible to directly confirm that the target alcoholate is produced by analysis, it requires complicated operations for isolation and purification. In addition, the alcoholate body of the said Formula (1) can be used for next reaction (2nd this invention) as it is.

  The second aspect of the present invention will be described below.

  In the second aspect of the present invention, the alcoholate compound (first raw material) represented by the formula (1) obtained in the first aspect of the present invention and a polymerizable unsaturated carboxylic acid anhydride or polymerizable unsaturated carboxylic acid halide (first The 2-cyanomethyl-2-adamantyl ester compound represented by the formula (4) is produced by including a step of reacting the two raw materials.

(Polymerizable unsaturated carboxylic acid anhydride and polymerizable unsaturated carboxylic acid halide)
The polymerizable unsaturated carboxylic acid anhydride used as the second raw material in the reaction of the second invention is represented by the following formula (5).

R ⁷ in the above formula (5) is a polymerizable unsaturated hydrocarbon group which R ⁷ may have a substituent. Specific examples of the polymerizable unsaturated hydrocarbon group include a vinyl group, an isopropenyl group, an allyl group, a 1-propenyl group, a 3-butenyl group, a 3-methyl-3-butenyl group, Examples include 4-pentenyl group and 1,3-butadienyl group.

  Specific examples of polymerizable unsaturated carboxylic acid anhydrides that can be suitably used in the present invention include acrylic acid anhydride, methacrylic acid anhydride, vinyl acetic acid anhydride, crotonic acid anhydride, 4-pentenoic acid anhydride, 4-Methyl-4-pentenoic anhydride, 5-hexenoic anhydride, 2,4-pentadienoic anhydride and the like can be mentioned. Among these compounds, acrylic acid anhydride or methacrylic acid anhydride is particularly preferable from the viewpoint of the usefulness of the product.

  In the reaction, a polymerizable unsaturated carboxylic acid halide represented by the following formula (6) can be used as the second raw material instead of the polymerizable unsaturated carboxylic acid anhydride.

X in the above formula (6) means a chlorine atom, a bromine atom, or an iodine atom. R ⁷ has the same meaning as in formula (5), and the preferred groups are also the same.

  Specific examples of polymerizable unsaturated carboxylic acid halides that can be suitably used in the present invention include acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, vinyl acetate chloride, Vinyl acetate bromide, vinyl acetate iodide, crotonic acid chloride, crotonic acid bromide, crotonic acid iodide, 4-pentenoic acid chloride, 4-pentenoic acid bromide, 4-pentenoic acid iodide, 4-methyl-4-pentenoic acid chloride, 4- Methyl-4-pentenoic acid bromide, 4-methyl-4-pentenoic acid iodide, 5-hexenoic acid chloride, 5-hexenoic acid bromide, 5-hexenoic acid iodide, 2,4-pentadienoic acid chloride, 2,4-pentadiene Phosphate bromide, 2,4-pentadiene acid iodide, or the like can be mentioned. Among these compounds, acrylic acid chloride, methacrylic acid chloride, acrylic acid bromide, and methacrylic acid bromide are preferable from the viewpoint of the usefulness of the product, and acrylic acid chloride and methacrylic acid chloride are particularly preferable from the viewpoint of availability.

  When the polymerizable unsaturated carboxylic acid anhydride is used as the second raw material, the amount used is 1 with respect to 1 mol of the first raw material (alcoholate of 2-cyanomethyl-2-adamantanol compound) for ease of post-treatment and the like. It is preferred to use from 10 to 10 mol, in particular from 1 to 5 mol. In addition, the amount used when the polymerizable unsaturated carboxylic acid halide is used as the second raw material is 1 to 1 mol per 1 mol of the first raw material (alcoholate of 2-cyanomethyl-2-adamantanol) for ease of post-treatment and the like. 10 mol, in particular 1 to 5 mol, are preferably used.

(Reaction conditions and reaction procedure)
The reaction can be suitably performed by mixing the first raw material and the second raw material. At this time, the reaction is preferably carried out in an organic solvent in order to facilitate control of the reaction conditions and efficiently obtain the desired product. Known organic solvents can be used without limitation, but from the viewpoint of easy availability and a large amount of target product, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, ethylene glycol dimethyl ether Ethers such as hexane, heptane, octane and cyclohexane; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; aromatics such as benzene, toluene and xylene Hydrocarbons etc. can be used conveniently. Among these, it is preferable to use at least one selected from the group consisting of diethyl ether, di-n-butyl ether and tetrahydrofuran. These organic solvents may be used as a mixture of two or more. The amount of the organic solvent to be used is not particularly limited, but it is preferable to use 1 to 100 parts by mass, particularly 2 to 50 parts by mass with respect to 1 part by mass of the first raw material because of ease of post-treatment.

  Moreover, in the said reaction, you may add a polymerization inhibitor in order to suppress the production | generation (byproduct) of an oligomer impurity. As the polymerization inhibitor, a known polymerization inhibitor can be used without limitation.

  The operating procedure for carrying out the reaction is not particularly limited. For example, by introducing a predetermined amount of each reactant (reactant) into the reaction vessel while controlling the temperature, and if necessary, introducing a solvent and an additive, and stirring. It can be suitably performed. At this time, the order of introduction of the reactants is not particularly limited, but when the alcoholate of 2-cyanomethyl-2-adamantanol compound is reacted with the polymerizable unsaturated carboxylic anhydride, the amount of by-products such as oligomer impurities produced In order to reduce this, it is preferable to add dropwise a solution of an alcoholate of 2-cyanomethyl-2-adamantanol compound in an organic solvent after charging a mixture of an organic solvent and a polymerizable unsaturated carboxylic acid anhydride into a reactor. .

  The reaction conditions for the reaction may be appropriately determined depending on the reaction system, but the reaction temperature is preferably 50 ° C. or lower, particularly −10 to 30 ° C. from the viewpoint of suppressing by-products such as oligomer impurities. is there. When the reaction is carried out in such a temperature range, a sufficient conversion rate can usually be obtained in 0.5 to 24 hours. The reaction can be carried out under pressure, under reduced pressure, or under normal pressure, but it is preferable to carry out under normal pressure for simplicity. In the above reaction, if water is mixed in the reaction solution, a side reaction occurs, which is not preferable. Therefore, after sufficiently replacing with an inert gas such as nitrogen or argon, the reaction is performed while venting the inert gas. Is preferred.

(2-cyanomethyl-2-adamantyl ester compound)
By carrying out the reaction in this manner, a 2-cyanomethyl-2-adamantyl ester compound represented by the following formula (4) is produced as a reaction product.

{Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as those in formula (1), and R ⁷ represents a polymerizable unsaturated hydrocarbon group which may have a substituent. is there. }
The various substituents in the formula (4) are uniquely determined according to the first raw material and the second raw material used in the reaction.

  Specific examples of the 2-cyanomethyl-2-adamantyl ester compound represented by the formula (4) include 2-cyanomethyl-2-adamantyl acrylate, 2-cyanomethyl-2-adamantyl methacrylate, 2 -Cyanomethyl-1-methyl-2-adamantyl acrylate, 2-cyanomethyl-1-methyl-2-adamantyl methacrylate, 2-cyanomethyl-5-methyl-2-adamantyl acrylate, 2-cyanomethyl-5-methyl-2-adamantyl methacrylate 2-cyanomethyl-1,3-dimethyl-2-adamantyl acrylate, 2-cyanomethyl-1,3-dimethyl-2-adamantyl methacrylate, 2-cyanomethyl-1,5-dimethyl-2-adamantyl acrylate, 2-cyanomethyl -1,5-dimethyl-2-adamantyl methacrylate, 2-cyanomethyl-1,7-dimethyl-2-adamantyl acrylate, 2-cyanomethyl-1,7-dimethyl-2-adamantyl methacrylate, 2-cyanomethyl-1,5, 7-trimethyl-2-adamantyl acrylate, 2-cyanomethyl-1,5,7-trimethyl-2-adamantyl methacrylate, and the like are mentioned. Of these, 2-cyanomethyl-2-adamantyl acrylate is particularly preferred from the viewpoint of ease of production. 2-cyanomethyl-2-adamantyl methacrylate, 2-cyanomethyl-5,7-dimethyl-2-adamantyl acrylate, and 2-cyanomethyl-5,7-dimethyl-2-adamantyl methacrylate are preferred.

(Separation and purification method)
The method for separating the target 2-cyanomethyl-2-adamantyl ester compound from the reaction solution obtained in the reaction step is not particularly limited, but for example, it can be suitably separated by the following method.

  That is, after the reaction is completed, an excess of the polymerizable unsaturated carboxylic acid anhydride or polymerizable unsaturated carboxylic acid halide is decomposed using an alkaline aqueous solution, washed with water, and if necessary, adsorption such as activated carbon treatment, silica treatment, alumina treatment, etc. It is preferable to separate by removing the solvent after the treatment and drying. By separating in this way, the content of the target 2-cyanomethyl-2-adamantyl ester compound is usually 50% by mass or more, and the 2-cyanomethyl-2-adamantanol compound as an impurity is 1% by mass. A crude product containing less than 50% by mass and optionally containing a trace amount of oligomer impurities can be obtained. In addition, you may perform the said water washing and adsorption processing after the solvent exchange which changes the kind of solvent. By performing the adsorption treatment, it is possible to efficiently remove a coloring component contained in a trace amount. In addition, the purity of the target product can be confirmed by measurement by gas chromatography (GC), and the amount of oligomer impurities can be confirmed by gel permeation chromatography (GPC).

  The crude product thus obtained can be purified further by a known method such as crystallization (recrystallization), vacuum distillation, steam distillation, sublimation purification or the like to obtain a high-purity target product. As a purification method, it is preferable to employ a crystallization method using a mixed solvent of alcohol and water as a crystallization solvent because a highly pure target product can be obtained simply and efficiently. The crystallization method is one of the general-purpose purification methods because of its simplicity of operation, but the target 2-cyanomethyl-2-adamantyl ester compound has a wide range of polar organic properties from high to low polarity. Since it dissolves in a solvent, the amount obtained is reduced when crystallization is performed using a commonly used organic solvent. On the other hand, when a mixed solution of alcohol and water is used as a crystallization solvent, the highly purified target product can be efficiently recovered. At this time, the mixing ratio (mass ratio) of alcohol and water in the mixed solution serving as a crystallization solvent is not particularly limited, but alcohol: water = 1: 0.01 to 1: 2, particularly 1: 0.1 to 0.1. It is preferably used at 1: 1.5.

  As the alcohol used in the above mixed solution, known alcohols can be used without limitation. From the viewpoint of availability, methanol, ethanol, propanol, isopropyl alcohol, n-butanol, t-butanol, n-pentanol, n- It is preferable to use at least one selected from the group consisting of hexanol and cyclohexanol. Among these, it is particularly preferable to use methanol, ethanol, or isopropyl alcohol because of its low price and high purity of the desired product.

  Although the usage-amount of alcohol is not restrict | limited in particular, 0.25-20 mass with respect to 1 mass part of 1st raw materials (alcoholate of 2-cyanomethyl-2-adamantanol compound) used at the reaction process from a viewpoint of collection | recovery efficiency. Parts, in particular 0.5 to 10 parts by weight, are preferred. Moreover, the usage-amount of water is 0.01-20 mass parts with respect to 1 mass part of 1st raw materials (alcoholate of 2-cyanomethyl-2-adamantanol compound) used at the reaction process for the same reason, Especially 0 is used. It is preferable to use 1 to 10 parts by mass.

  Crystallization using the above crystallization solvent involves crystallization of the crude product or a primary purified product (hereinafter also referred to as a crude product) obtained by subjecting the crude product to a simple purification treatment such as adsorption treatment. Add the remaining components of the crystallization solvent after mixing the solvent or mixing the crude product and one component of the crystallization solvent to dissolve the crude product, or add one of the crude product and the crystallization solvent. The solution is prepared by mixing the ingredients and dissolving the crude product once, cooling and precipitating the crystals, and then adding the remaining components of the crystallization solvent, or mixing the solution of the crude product and the crystallization solvent. From the target crystal. At this time, the method for adding the alcohol and water is not particularly limited, and may be used by mixing in advance, or the alcohol and water may be added separately, but in some cases, 2-cyanomethyl-2-adamantyl ester Since there is a possibility that the compound does not crystallize and becomes oily, adding the alcohol first, cooling and precipitating the crystal, then adding water gives the target product in high yield and high purity. Therefore, it is preferable. In this case, the time for adding water is not particularly limited, but may be added whenever crystal precipitation is observed.

  The temperature at which crystallization is performed is not particularly limited, but is preferably 20 ° C. or less, particularly 10 ° C. or less, because there are many objects to be obtained, and the crystallization time is not particularly limited. In general, the target product can be obtained in high yield and purity in 0.5 to 24 hours. For example, after adding methanol to the crude body, etc., after cooling to 10 ° C. or less to precipitate crystals, aging for about 1 to 2 hours and then adding water so that the liquid temperature does not exceed 10 ° C., A target crystal is precipitated by aging for 1 to 2 hours, and the obtained crystal is recovered by filtration or the like, whereby a 2-cyanomethyl-2-adamantyl ester compound having a purity of 95% by mass or more can be obtained.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
The inside of the 500 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. Next, in the flask, 55 ml (0.11 mol, 1.1 mol times of 2-adamantanone used) of lithium diisopropylamide (manufactured by Aldrich, concentration 2.0 mol / l) and 90 g of tetrahydrofuran (of 2-adamantanone used). 6 weight times) was added and cooled to 0 ° C. After stirring for 5 minutes, 4.56 g of acetonitrile (0.11 mol, 1.1 mol times of 2-adamantanone used) was added so as not to exceed 5 ° C. The solution became a brown slurry from a brown homogeneous solution. After stirring for 5 minutes, a mixed solution of 1-5.0 g (0.10 mol) of 2-adamantanone and 45 g of tetrahydrofuran (3 mass times of 2-adamantanone) was added dropwise so that the reaction solution did not exceed 5 ° C. After aging for 30 minutes, the solution had a green uniform state. As a result of sampling and GC analysis, the content of 2-cyanomethyl-2-adamantanol is GC purity 82%, the raw material 2-adamantanone is 10%, and 2-cyanomethyleneadamantane is 8%. It was.

Example 2
The inside of the 500 ml four-necked flask was sufficiently replaced with argon gas and vented. Next, 0.76 g of lithium (0.11 mol, 1.1 mol times of 2-adamantanone used), 20 g of tetrahydrofuran (1.33 mass times of 2-adamantanone used), and 10 g of heptane (used) in the flask. 2-adamantanone 0.67 mass times) and stirred at room temperature. After 5 minutes, 11.13 g of diisopropylamine (0.11 mol, 1.1 mol times of 2-adamantanone used) and 5.73 g of styrene monomer (0.055 mol, 0.55 mol of 2-adamantanone used) ) Was added dropwise so that the temperature of the reaction solution did not exceed 30 ° C. After completion of the dropwise addition, the reaction solution was an orange uniform solution. Thereafter, the reaction solution was cooled to 0 ° C., and 4.56 g of acetonitrile (0.11 mol, 1.1 mol times 2-adamantanone used) was added so as not to exceed 5 ° C. The solution became a brown slurry from a brown homogeneous solution. After stirring for 5 minutes, a mixed solution of 15.0 g (0.10 mol) of 2-adamantanone and 45 g of tetrahydrofuran (3 mass times of 2-adamantanone) was added dropwise so that the reaction solution did not exceed 5 ° C. After aging for 30 minutes, the solution had a green uniform state. As a result of sampling and GC analysis, the 2-cyanomethyl-2-adamantanol content was 60% GC purity, the raw material 2-adamantanone was 30%, 2-adamantanol was 2%, 2-cyano It contained 10% methylene adamantane.

Example 3
The inside of the 500 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. Next, 90 g of tetrahydrofuran and 11.13 g (0.11 mol) of diisopropylamine were charged into the flask and cooled to −10 ° C. Thereafter, 68.75 ml (0.11 mol) of n-butyllithium (1.6 mol / l manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the reaction solution did not exceed -10 ° C. The solution was a pale yellow homogeneous solution. After stirring for 5 minutes, 4.56 g (0.11 mol) of acetonitrile was added so that the reaction solution did not exceed −10 ° C. After completion of the addition, the reaction solution was in the form of a white slurry. After stirring for 5 minutes, a mixed solution of 1-5.0 g (0.10 mol) of 2-adamantanone and 45 g of tetrahydrofuran was added dropwise so that the reaction solution did not exceed -10 ° C. After aging for 30 minutes, the solution had a yellow uniform state. As a result of sampling and GC analysis, the content of 2-cyanomethyl-2-adamantanol is GC purity 90%, the raw material 2-adamantanone is 9%, and 2-cyanomethyleneadamantane is 1%. It was.

Example 4
The inside of the 500 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. Next, 90 g of tetrahydrofuran and 11.13 g (0.11 mol) of diisopropylamine were charged into the flask and cooled to 0 ° C. Thereafter, 68.75 ml (0.11 mol) of n-butyllithium (1.6 mol / l manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the reaction solution did not exceed 5 ° C. The solution was a pale yellow homogeneous solution. Next, a mixed solution of 15 g (0.11 mol) of 2-adamantanone, 4.56 g (0.11 mol) of acetonitrile and 45 g of tetrahydrofuran was added dropwise to the solution so that the reaction temperature did not exceed 5 ° C. After aging for 4 hours, the solution had a yellow uniform state. As a result of sampling and GC analysis, the content of 2-cyanomethyl-2-adamantanol is GC purity 90%, the raw material 2-adamantanone is 7%, and 2-cyanomethyleneadamantane is 3%. It was.

Example 5
The inside of a 500 ml four-necked flask (referred to as “Kan 1”) was sufficiently replaced with nitrogen gas and aerated. Next, 90 g of tetrahydrofuran and 11.13 g (0.11 mol) of diisopropylamine were charged into the flask and cooled to 0 ° C. Thereafter, 68.75 ml (0.11 mol) of n-butyllithium (1.6 mol / l manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the reaction solution did not exceed 5 ° C. The solution was a pale yellow homogeneous solution. The inside of a separately prepared 500 ml four-necked flask (referred to as “kettle 2”) was sufficiently replaced with nitrogen gas and vented, and then 15 g (0.11 mol) of 2-adamantanone and 4.56 g of acetonitrile ( 0.11 mol) and 45 g of tetrahydrofuran were introduced and stirred at 0 ° C. The solution of the organometallic compound in the kettle 1 was dropped into the kettle 2 so that the reaction temperature did not exceed 5 ° C. After aging for 2 hours, the solution had a yellow uniform state. As a result of sampling and GC analysis, the content of 2-cyanomethyl-2-adamantanol is GC purity 98%, the raw material 2-adamantanone is 1%, and 2-cyanomethyleneadamantane is 1%. It was.

Example 6
The inside of the 500 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. Next, 19.5 g (0.12 mol, 1.2 mol times of 2-adamantanone used in Example 4) of pure methacrylic anhydride (purity 95% by mass) was added to the flask, and tetrahydrofuran was methacrylic anhydride. The same amount of 19.5 g was added and stirred, and cooled to 0 ° C. Thereto was added dropwise a solution containing lithium 2-cyanomethyl-2-adamantanolate obtained in Example 4 so that the reaction solution did not exceed 10 ° C. After stirring for 1 hour, it was washed twice with 40 g of a 5% aqueous sodium hydroxide solution, and the organic layer was concentrated under reduced pressure to obtain 25 g of a viscous product. As a result of performing GC analysis on this viscous product, the viscous product was found to be the target product of 2-cyanomethyl-2-adamantyl methacrylate 67%, 2-cyanomethyl-2-adamantanol 18%, 2-adamantanone 7% 2-cyanomethylene adamantane 8%.

Example 7
In Example 6, the reaction was performed in the same manner except that 15.8 g (0.12 mol) of acrylic anhydride (purity 95% by mass) was used instead of methacrylic anhydride. After concentration, 23 g of viscous material was obtained. As a result of GC analysis, the viscous product was 68% 2-cyanomethyl-2-adamantyl acrylate, 17% 2-cyanomethyl-2-adamantanol, 7% 2-adamantanone, 2-cyano It contained 8% methylene adamantane.

Example 8
The inside of the 500 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. Next, 19.5 g (0.12 mol, 1.2 mol times of 2-adamantanone used in Example 5) and 19.5 g of tetrahydrofuran were added to the flask with methacrylic anhydride (purity 95% by mass) in a pure content. Stir and cool to 0 ° C. Thereto was added dropwise a solution containing lithium 2-cyanomethyl-2-adamantanolate obtained in Example 5 so that the reaction solution did not exceed 10 ° C. After stirring for 1 hour, it was washed twice with 40 g of a 5% aqueous sodium hydroxide solution, and the organic layer was concentrated under reduced pressure to obtain 28 g of a viscous product. As a result of GC analysis, the viscous product was found to be 91% of the target 2-cyanomethyl-2-adamantyl methacrylate, 6% 2-cyanomethyl-2-adamantanol, 1% 2-adamantanone, 2-cyano It contained 2% methylene adamantane.

Example 9
In Example 8, the reaction was performed in the same manner except that 15.8 g (0.12 mol) of acrylic anhydride (purity 95% by mass) was used instead of methacrylic anhydride. After concentration, 24 g of viscous material was obtained. As a result of GC analysis, the resulting viscous product was 90% 2-cyanomethyl-2-adamantyl acrylate, 7% 2-cyanomethyl-2-adamantanol, 1% 2-adamantanone, 2- It contained 2% cyanomethylene adamantane.

Example 10
In Example 8, the reaction was conducted in the same manner except that 12.5 g (0.12 mol) of methacrylic acid chloride was used instead of methacrylic anhydride. After concentration, 28 g of viscous material was obtained. As a result of GC analysis, the resulting viscous product was 91% 2-cyanomethyl-2-adamantyl methacrylate, 6% 2-cyanomethyl-2-adamantanol, 1% 2-adamantanone, 2- It contained 2% cyanomethylene adamantane.

Example 11
In Example 9, the reaction was carried out in the same manner except that 10.9 g (0.12 mol) of acrylic acid chloride was used instead of acrylic acid anhydride. After concentration, 24 g of viscous material was obtained. As a result of GC analysis, the resulting viscous product was 90% 2-cyanomethyl-2-adamantyl acrylate, 7% 2-cyanomethyl-2-adamantanol, 1% 2-adamantanone, 2- It contained 2% cyanomethylene adamantane.

Example 12
To 28 g of the viscous material obtained in Example 8, 45 g of heptane and 1.5 g of activated carbon were added and stirred at room temperature for 1 hour. Thereafter, the activated carbon was filtered off, the organic layer was concentrated under reduced pressure, and washed with 45 g of ion-exchanged water until the pH became neutral. Add 22.5 g of 1.5 mass times of 2-adamantanone used as a raw material in Example 5 (1.3 weight times in terms of alkoxide compound of 2-cyanomethyl-2-adamantanol) and stir at room temperature. Then, after forming a uniform solution, the solution was cooled to 5 ° C. to precipitate crystals and aged for 1 hour. Thereafter, 7.5 g (0.4 mass times in terms of an alkoxide compound of 2-cyanomethyl-2-adamantanol), which is 0.5 times the weight of 2-adamantanone using ion-exchanged water as a raw material in Example 5, It was dripped so that it might not exceed 10 degreeC. After dropping, the mixture was aged at 5 ° C. for 1 hour and filtered to obtain 20 g of a white solid of 2-cyanomethyl-2-adamantyl methacrylate (yield 77% in terms of 2-adamantanone). As a result of analyzing the obtained solid by GC and GPC, the content of 2-cyanomethyl-2-adamantyl methacrylate was GC purity of 98%, and the content of oligomer impurities in terms of polystyrene was 0.2% by mass.

Examples 13-17
In Example 12, it carried out similarly except having changed the quantity of used alcohol and water into Table 1. The results are shown in Table 1. The amount of the solvent used is shown on the basis of 2-adamantanone used in Example 5.

Example 18
28 g of the viscous material obtained in Example 10 was post-treated and crystallized in the same manner as in Example 12, and 20.0 g of 2-cyanomethyl-2-adamantyl methacrylate white solid (in terms of 2-adamantanone) was obtained. (Yield 77%). As a result of analyzing the obtained solid by GC and GPC, the content of 2-cyanomethyl-2-adamantyl methacrylate was GC purity of 98%, and the content of oligomer impurities in terms of polystyrene was 0.2% by mass.

Examples 19-23
It carried out similarly except having changed the quantity of the alcohol and water used in Example 18 into Table 2. The results are shown in Table 2. The amount of the solvent used is shown on the basis of 2-adamantanone used in Example 5.

Reference example 1
The inside of the 500 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. Tetrahydrofuran (60 g) (4 weight times of 2-adamantanone used) was added and cooled to 0 ° C. n-Butyllithium (1.6 mol / l manufactured by Wako Pure Chemical Industries, Ltd.) 68.75 ml (0.11 mol, 1.1 mol times 2-adamantanone used) so that the reaction solution does not exceed 5 ° C. Added to. The solution was a pale yellow homogeneous solution. After stirring for 5 minutes, 4.56 g of acetonitrile (0.11 mol, 1.1 mol times of 2-adamantanone used) was added so that the reaction solution did not exceed 5 ° C. After the addition, the reaction solution was in the form of a white slurry. After stirring for 30 minutes, a solution of 15 g (0.11 mol) of 2-adamantanone and 45 g of tetrahydrofuran (3 times by weight of 2-adamantanone used) was added dropwise so that the reaction solution did not exceed 5 ° C. After completion of the dropwise addition, the reaction solution was a uniform yellow solution. As a result of sampling and GC analysis after aging for 1 hour, the content of 2-cyanomethyl-2-adamantanol was GC purity 45%, the raw material 2-adamantanone was 43%, and 2-cyanomethyleneadamantane was 2% was included.

Reference example 2
In Example 12, instead of methanol and ion-exchanged water as a crystallization solvent, octane was 45 g of 3 mass times of 2-adamantanone used in Example 5 (2 in terms of alkoxide of 2-cyanomethyl-2-adamantanol). .6 times) and stirred at room temperature to obtain a uniform solution, cooled to 5 ° C. to precipitate crystals, and aged for 1 hour. Thereafter, filtration was performed to obtain 5.8 g (yield 25% in terms of 2-adamantanone). As a result of analyzing the obtained solid by GC and GPC, the content of 2-cyanomethyl-2-adamantyl methacrylate was 92% GC purity, and the content of oligomer impurities in terms of polystyrene was 0.9% by mass.

Claims (3)

Following formula (1)

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A is an alkali metal.)
A process for producing an alcoholate compound represented by
Following formula (2)

{Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as those in the formula (1). }
And an adamantanone compound represented by formula (3):

(In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A is an alkali metal.)
The process characterized by including the process with the organometallic compound shown by these. Following formula (4)

{Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as those in formula (1), and R ⁷ represents a polymerizable unsaturated hydrocarbon group which may have a substituent. is there. }
A process for producing an alcoholate compound represented by the formula (1) by the method according to claim 1, and an alcoholate obtained in the process A method comprising reacting a compound with a polymerizable unsaturated carboxylic acid anhydride or a polymerizable unsaturated carboxylic acid halide. The method according to claim 2, wherein the reaction between the alcoholate compound and a polymerizable unsaturated carboxylic acid anhydride or a polymerizable unsaturated carboxylic acid halide is performed by using the polymerizable unsaturated carboxylic acid anhydride or the polymerizable unsaturated carboxylic acid. A method comprising adding the alcoholate compound to a solution containing an acid halide.